Process and apparatus for the conversion of heavy petroleum oils into lighter oils



13 1927. 1,642,624 Sept v. w. NORTHRUP PROCESS AND APPARATUS FOR THE CONVERSION OF HEAVY PETROLEUM OILS INTO LIGHTER OILS Original Filed NOV. 20, 1924 Verrzan W lfariizrup Patented Sept. 13, .1927,

:v ii STATES PATENT OFFICE.

vEnNoN w. Noarnnur, or nuntocx, MARYLAND, ASSIGNOB TO THE rErRoLEUm HYDROGENA'IION COMPANY or AmEmcA, INCORPORATED, or WILMINGTON, DELL! WARE, A'COBPORATION OF rEooEss ND-APPARATUS ron 'rnE CONVERSION or 3mm? PETROLEUM 011s m re mourns, OILS.

Y Application flied November at, 1924,seria1 N6. 751,171. Renewed February a, 1927.

thereby fixing the reaction mass into a new,

10 permanent compound or compounds of the natureof lower boiling petroleum oils, as hereinafter set forth.

Any crude petroleum oil as drocarbons, very nearly alike as regards percentages'of hydrogen and carbon, but with widely difi'erent boiling points, and in ordinary refining these various hydrocarbons are separated b distillation into varying groups or cuts 0 fractions boiling within certain ranges, commercially known as gasoline, kerosene, gas-oil, fuel oil, etc. Of these cuts, gasoline is at the present time the most valuable, and for this reason various methods have been devised to crack the heavier cuts into the lighter ones.

Cracking processes, in the main, have consisted of some method of subj ecting these heavy cuts, either in the vapor or liquid phase, to an amount of heat and pressure suflicient for their decomposition, thus liberating the hydrogen in the form of a non-' condensable gas, and the carbon in the form of still higher boiling oils or coke. The gasoline yields in these cracking processes are 7 poor as there is not enough hydrogen present in any petroleum oil to give in this way any large percentage of gasoline, as the gases which are necessarily formed through this destructive distillation are much richer in hydrogen than gasoline, and the oils remainof gasoline result from the treatment. of the heavy petroleum oil according to my invention.

As is well known, there is but a small ercentage more of hydrogen in gasoline t an mixture of it comes from the ground is a complex of numerous hy-- day gasoline is probably composed mostly of h'eptane ((3 11 which contains but about one-half of one percent (0.51 more hydrogen than kerosene (decane, C The addition of only a very small percentage of hydrogen is, therefore, theoretically necessary to convert the heavier fractions of crude oil into lighter and lower boiling point compounds. a I

.For supplying this hydrogen, I may use any source thereof, but I prefer either hydrogen itself or natural gas which usually consists principally of methane (CI-I amples .of the sum total of the reactions takmg place are probably as set forth in the following equations, but it is to be understood that my invention is not to be limited thereby:

Theoretically, my invention seems be which apparently ioniz'e the vapors of petroleum oils and impart to them. a high con ductivit'y. Free ions seem to be present to a large extent in both the lighter and heavier petroleum vapors, rendering them exceedingly susceptible to electrical influences and whereby they are converted into charged ions, and the electrical field to which I sub-. ject the vapors in my process is such as apparently to have an influence upon the electrons and ions, atoms and molecules, present inthe vapors of the higher boiling oils and of the hydrogen-rich gas, causing some form of rearrangement of particles and charges,

and is, according to this theory, suflicient'to causechanges, such, for example, as electronic interchange between the ions in the higher boiling petroleum vapors and the hydrogen-rich gas to form the constituents into new groups and to influence the molecular structure and rearrangement of the atoms in the molecules, whereby a reaction mass is produced, which is very easily catain kerosene or fuel oil. For instance, present lyzed into permanent compounds of the nature of gasoline, the catalyst being heated to a a temperature below which ordinary cracking or destructive distillation takes place.

Referring to the drawing, the figure'is a 5 partially diagrammatic side view, partly in elevation and partly'in section, of my appa-- r'atus.

I provide a still A which is suitably heated to convert heavier petroleum hydrocar- I0 bons therein into vapors, which vapors rise I up through the tube B connected to the still.

The tube B has an opening in the top thereof in which an insulator E is tightly fitted, which supports an electrode wire '1) sub- 16 stantially centrally of the tube B,-this electrode being held taut'centrally of the tube by a bob T of non-conductin material at the lower free end thereof, an such bob 1s preferablyfluted to permit the free passage- 2 of gas. An inletgpipe O surrounds the lower endof the tube B and is connected therewith by a series of openings 0, by means of which hydrogen-rich gas, such as hydrogen, niethane, natural gas, etc., is led into the lower end of the'tubeB to mix with the -hydro-' carbon vapors therein, means bein provided such as the valve C" for proper y controlling the proportions of hydrogen-richgas.

' A conductin member from which-the wire electrode D epends passes through the insulator E and one terminal of asource of high tensionelternating electric current is connected therewith as at F, the other terminal vapor-gas mixture to travel throughout the length of the catalyzer in a thin annular stream, the functions of the corrugationsbeing to cause'swirling movements in this stream in order vto efl'ect maximum contact of the gas-vapor mixture with the catalyzer surface. i

v The opposing surfaces of the tubes I and J may be composed of or coated with cataly'tic material, such as nickel, cobalt. palladium, aluminum, .iron, etc., or mixtures thereof, a very eflicient catalyst being nickel containing about 5% of iron and 5% of aluminum, such catalytic surfaces being rendered more active by the heating meansaforesaid.

- The cat lyzed mixture then asses by means of t e pipe L to the dep egmatin tower orcolumnM which is of the usua inverted cup type, and from this they pass through the pipe N to the at of. the cooler amps;

0 of the usual tube type. A cooling medium, preferably a high' boiling petroleum oil, is maintained at a temperature of about 200 F. to 400 F. and is circulated around the exterior of pipes U of the cooler O by means of the inlet and outlet pipes O. This will effect suflicient cooling but will nevertheless permit the gasoline-like compounds produced to pass out through the pipe Q, in the vapor state, the temperatures of the cooler O and the column M being thereby suitably .maintained for this purpose. The bottom ends of the pipes U lead to a chamber in the bottom of the cooler which is connected by the pipe Q to a condenser Q, which in turn is connected by pipe R to the tail house and finished product storage tanks, which are not shown. A trap -P connects the bottom chamber of the cooler O with the top of the tower M, v

The vapors of higher boiling points are condensed inthe column M and pass to the bottom thereof as is usual in such columns nto such column and any liquid passin through the pipe L oes not rise therethrough. Furthermore, vapors condensed in the cooler 0, after passing through'the trap P, pass gradually downwardly through the column M to the bottom thereof; and all the liquids" which are not of gasoline boiling points and whiclipass to the bottom of the column M flow. therefrom through pipe S backto the still A. from such source of current being connected 7 Various 'types of electric treatment for the conversion of petroleum hydrocarbons have already been proposed, for example, to impress an electric-current of high density or high frequency, upon petroleum vapors or mixtures of petroleum vaporsand a'ghydrogen-rich gas, to effect by the use of such high density current, or such high frequency current, alone, a cracking action, without,

however, combining the same with catalytic action; or to treat a mixture of heavier hydrocarbon vapors and a hydrogen-rich gas by subjecting the same to the effect of a cata: lyst which is subjected to a sparking treatment to keep it clean. In such processes, it is, however, necessary to use an electric current of such intensity that the results hoped for cannot be successfully obtained;

.for as a matter of fact, a current of sufficient voltage to form a brush discharge or sparking discharge is far too disruptive for the successful accomplishment of the purpose of my invention.

- According to my invention, I usean electric current of a potential merely suflicient to create a strong electrostatic field bet-ween the walls of the electrolyzer tube B and electrode D coaxial therewith; that is, a field merely strong enough to be eflicient to ionize the particles therebetween. In practice, the tube B should be of suflicient length to thoroughly ionize the molecules present in the mixture to be later acted upon by the catalytic material, and I have found that for eight (8) catalytic converters containing seventy-two (72) tubes each, sixteen (16) catalyzer tubes of an inside diameter of two and onevhalf (2 inches and eighteen (18) inches long are quite effective. This eflects thorough electronization of the charge of oil and hydrogen-rich gas and has been found to be sufficient with from 4 to 6 pounds usual still pressure, with aclearance of about three-thirty-seconds of an inch between the ribbed tube and other catalytic tube; and when operating at temperatures hereinafter specified the resulting effect is such as to produce very high yields of gasoline from fuel oil and kerosene, without the formation of any soot or carbon at any place in the system. I

In the operation of my process heavier vapors rise from the heated oil in the still A into the tube B with which is admixed, at the bottom of tube B by means of the inlet pipe C, the proper amount of hydrogen or hydrogen-rich gas to form lighter hydrocarbons of the same series of the lighter boiling points desired later in the process. Upon this mixture of vapor. and gas, an electric current is impressed sufiicient only to cause electrons to be. set free and to move about and thoroughly ionize both molecules of the gas and those of the heavier oil vapors, thus throwing the entire mixture into ionic disorder and giving to the relative components as completely an electrostatic charge as is possible, forwhat is generally desired at this stage of the process is that each molecule in the entire mixture be given the correct electric charge to enable all ions and molecules present to maintain "equilibrium, at least temporarily, so that later in the process the catalytic material will assist the breaking, up of the heavy hydrocarbons into simpler structures of lower boiling points, without cracking the component molecules, it being my object to place the lighter. hydrogen molecules 'or atoms of the other light hydrocarbon in such a state with regard to the heavy oil mo ecules that ready adoption can take place under the effect of the catalyst to form gasoline-like materialas to specific gravity and boiling ints.

It is to be clearly understood that at this stage of the process there has not been enough electric potential 61' current 7 im pressed upon the mixture up to the time of their passing from the tube B to have caused any substantial cracking or chemical change, since vapors passing from the pipe H which are condensed to liquid have substantially the same composition as the mixture entering the tube B from the still A.

The thoroughly ionized mixture passes into the catalyticchamber which is heated sufiiciently to render the catalytic surfaces very active and there a change takes place between the hydrogen-rich gas and the heavy hydrocarbon vapor present, compounds of gasoline-like boiling. points being produced. A complete change from heavier hydrocarbons 'to lighter hydrocarbons does not take place instantaneously throughout the mass on subjection to a catalytic surface, nor does it usually take place as a rule as a result of one electric treatment followed by one catalytic treatment, and I have found that frequently from four (4) to eight (8) successive passes or combination of'steps mentioned are required, the number depending to some extent upon the final product desired. The vapors of the newly formed compound thus pass along 'into the dephlegmating tower, M, and into the storage tank, as alreadydescribed.

The number of ions produced is dependent upon the intensit of the electric discharge and varies wit different crude oils, some being slightly more ionizable' than .others'. I generally provide means for varying the potential and density of the electric current, so that it will range from about 2000 volts to 8000 volts, as desired. Two nonanes, alpha (0.) and beta (B) are the primary con-- stituents of kerosene orgasoline which are composed almost wholly of paraffins C I-1 -I have found that with Pennsylvania oils, an intensity of 3000 volts is generally sufficient to produce the necessary ionization. I have found that Oklahoma and Texas oils can be satisfactorily treated 1 according to my invention with about 4000 volts, but the Russian and Roumanian' petroleum oils containing naphthenes require about 4200 to 6000 volts.

The temperature of the catalyst is important and it has two functions, namely to activate the catalyst and to do soat a temperature below which active crackin or complete dissociation of the heavy petro eum molecules can take place. For example, for Pennsylvania oils, it is best that such tem- "peratures be below 900 F., and for mid- -catalytic action at a suitable temperature.

In practice I prefer to use eight (8) converters' having seventy-two (72) catalytic tubes per converter on one still having a charging capacity of 250 to 500 barrels, and when hydrogenating Penns lvani'a fuel oil into United States Motor S ecification gas olin'e to produce the various percentagesoi the different boiling points and gravltles,

as such gases must have, I maintain thecat final converter at about 800 F., using about five-eighths of a cubic foot of natural gas per gallon of gasoline made. When converting Oklahoma or Texas fuel or crude oil into gasoline the relative converter should .be maintained from to 300 F. higher than for-the case of Pennsylvania petro eum,

cubic foot of natural gas should be admitted at the electrolyzers for each gallon of gaso line finally produced.

What I claim is:

1. The method of converting heavier hydrocarbons into lighter hydrocarbons which comprises producing a mixtureof vapors of said heavier hydrocarbons anda as having available hydrogen, passingt e mixture through an electrifying zone and thereafter through a catalyzing zone which 1s independent of said electrif ing zone.

2. The method of converting heavier hydrocarbons into lighter hydrocarbons WhlCh comprises producing a. mixture of-vapors of said heavier hydrocarbons and a gas having available hydrogen, passing the mixture through an ionlzing zone and thereafter through a catalyzing zone which 1s mdependent of said 1oniz1ng zone.

3. The method of converting heavier hydrocarbons into lighter hydrocarbons whlch comprises producmg a mixture of vapors of said heavier hydrocarbons and a gas having available hydrogen, electrifying the mixture without substantial crackin taking place, and then catalyzing .the mlxture In a zone which is independent of the electrifying locus. D

4.; The method ,of converting heavier hy- .;-drocarbonslinto lighter hydrocarbons which.

compr ses producing a mixture otvapors of said heavier hydrocarbons and a gas having available hydrogen, ionizing the mixture without substantial cracking takmg place, and then catalyzing the mlxturaln a zone which is independent of the iomzing locus.

5. The method of converting heavierhydrocarbons into lighter hydrocarbons which comprises producing a mixture of vapors of said heavier hydrocarbons and a gas having available hydrogen, electrifying the mixture without substantial cracking in one zone, and then causing permanent conversion in another zone which is independent of said first mentioned zone. I

6. The method of converting heav1er hydrocarbons into lighter hydrocarbons which temperatures of the and from three- 1 fourths to seven-eighths of a' neeasae comprises producing a mixture of vapors of said heavier hydrocarbons and a-gas aving available hydro en, ionizing the mixture without 'substantia crackmg in one zone,

and' then-causin rmanent conversion 1n another zone wh c 1s independent of said first mentioned zone.

7., The method of converting heavier hy- I volts in one zone, whereby the reaction mass is electrified without substantial cracking taking place, and then catalyzing in another zone which is independent of saadfirst mentioned zone. i

8. The method of converting heavier hydrocarbons into lighter hydrocarbons which comprises producing amixture of vapors of said heavier hydrocarbons and a gas having available-hydrogen, subjecting the same to an alternatmg current field of 2000 to 8000 "olts in one zone, whereby the reaction mass is electrified without substantial cracking taking place, and then catalyzing at temperatures of about 725 F. to 1000 F. in another zone which is independent of said first mentioned zone.

9. The method of cracking heavier hydrocarbons into lighter hydrocarbons which comprises producing a mixture of vapors of said heavier hydrocarbons and a gas having available hydrogen, electrifying the mixture without substantial cracking taking place in one zone, and then catalyzing the cracking reaction in another zone whichis independent of said first mentioned zone.

10. The method of cracking heavier hydrocarbons into lighter hydrocarbons which comprises producing a mixture of vapors of said heavier hydrocarbons and a gas having available hydro en, ionizing the mixture without substantial cracking taking place 1n one'zone, and then catalyzing the cracking reaction in another zone which is independent of said first mentioned zone.

11. In an apparatus for converting heavier oils into lighter oils, an ionizing chamber, a catalyzing chamber directly connected therewith, means to maintain the catalyst at efiicient temperature, and means to separate out the desired fraction.

12. In an apparatus for converting heavier oils into lighter oils, an electrifying chamber, a catalyzing chamber directly connected therewith, means to maintain the catalyst at efficient temperature, and means to separate out the desired fraction.

13. In an apparatus for converting heavier oils into lighter oils, a still, an ionizer connected with the still, a catalyzer' directly connected with the ionizer, means to separate out the desired fraction, and means masses to return the undesired fraction to the still.

14. In an a aratus for converting heavieroils into ghter oils, a. still, an electrifier connected with the still, a catalyzer directly connected with the eleetrifier, means to separate out the desired fraction, and means to return the undesired fraction to the still. e

15. In an apparatus for converting Heavier oils into li hter a still, an ionizer connected wi the sti a catalyzer directly connected with the ionizer, means to maintain the catalyzer at eficient temperature, means to separate out the desired fraction, and means to return .the undesired fraction to the still. 7 I

l6. In an a aratus for converting heavier oils into lghter oils, a still,'an electrifier connected with the still, a catalyzer directl connected with the-electrifier, means to maintain the catalyzer at eflicient temrature, means to separate out the desired ction, and means to return the undesired fraction to the still.

VERNON W. NQRTHRUP. 

